Organometallics
Article
Synthesis of N-(4-(Dimesitylboryl)phenyl)benzenamine (3a). The
quantities involved and characterization data are as follows: (4-
bromophenyl)dimesitylborane31 (1.00 g, 2.48 mmol), aniline (0.30
mL, 3.22 mmol), potassium tert-butoxide (360 mg, 3.22 mmol), 1,1′-
bis(diphenylphosphino)ferrocene (dppf) (14 mg, 0.03 mmol), and
Pd(OAc)2 (28 mg, 0.03 mmol). The crude product was purified by
column chromatography over neutral alumina using hexane/ethyl
acetate (90/10) as eluent to produce the compound as an off-white
powder. Yield: 68% (700 mg). 1H NMR (400 MHz, CDCl3, 25 °C): δ
(ppm) 7.33- 7.31 (m, 2H), 7.29- 7.27 (m, 2H), 7.19- 7.17 (m, 2H),
7.09−7.01 (m, 1H), 6.96- 6.94 (m, 2H), 6.82 (s, 4H), 6.01 (br s, 1H),
2.31 (s, 6H), 2.07 (s, 12 H). 13C NMR (100 MHz, CDCl3, 25 °C): δ
(ppm) 147.9, 142.4, 141.5, 140.0, 138.4, 137.2, 129.9, 128.5, 123.2,
120.6, 118.3, 115.0, 24.0, 21.7. ESI-MS (positive ion mode): calcd for
C30H32BN 417.2628, observed 418.2709 (M + H)+.
Synthesis of Bis(4-(dimesitylboryl)phenyl)amine (4a). The quanti-
ties involved and characterization data are as follows: (4-
bromophenyl)dimesitylborane31 (1.00 g, 2.48 mmol), 4-
(dimesitylboryl)benzenamine22a (1.10 mg, 3.22 mmol), potassium
tert-butoxide (360 mg, 3.22 mmol), 1,1′-bis(diphenylphosphino)-
ferrocene (dppf) (14 mg, 0.03 mmol), and Pd(OAc)2 (28 mg, 0.03
mmol). The crude product was purified by column chromatography
over neutral alumina using hexane/ethyl acetate (95/5) as eluent to
produce the compound as an off-white powder. Yield: 48% (800 mg).
1H NMR (400 MHz, CDCl3, 25 °C): δ (ppm) 7.47−7.45 (m, 4H),
7.08−7.06 (m, 4H), 6.81 (s, 8H), 6.24 (s, 1H), 2.30 (s, 12H), 2.04 (s,
24H).13C NMR (100 MHz, CDCl3, 25 °C): δ (ppm) 145.9, 142.2,
141.2, 139.6, 138.8, 138.6, 128.5, 117.0, 23.9, 21.6. ESI-MS (positive
ion mode): calcd for C48H53B2N 665.4364, observed 666.4444 (M +
H)+.
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ASSOCIATED CONTENT
* Supporting Information
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The Supporting Information is available free of charge on the
Experimental, computational, crystallographic, and opti-
cal characterization details (PDF)
Accession Codes
mentary crystallographic data for this paper. These data can be
contacting The Cambridge Crystallographic Data Centre, 12
Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.
AUTHOR INFORMATION
Corresponding Author
*P.T.: tel, +91-080-2293-3353; fax, +91-23601552; e-mail,
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(8) (a) Liu, X.; Zhang, Y.; Li, B.; Zakharov, L. N.; Vasiliu, M.; Dixon,
D. A.; Liu, S.-Y. Angew. Chem., Int. Ed. 2016, 55, 8333−8337.
(b) Ishibashi, J. S. A.; Dargelos, A.; Darrigan, C.; Chrostowska, A.; Liu,
(9) (a) Braunschweig, H.; Celik, M. A.; Hupp, F.; Krummenacher, I.;
ORCID
Notes
The authors declare no competing financial interest.
Mailander, L. Angew. Chem., Int. Ed. 2015, 54, 6347−6351.
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(b) Braunschweig, H.; Geetharani, K.; Jimenez-Halla, J. O. C.;
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(10) Wang, X.-Y.; Narita, A.; Feng, X.; Mullen, K. J. Am. Chem. Soc.
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ACKNOWLEDGMENTS
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(11) Krieg, M.; Reicherter, F.; Haiss, P.; Strobele, M.; Eichele, K.;
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P.T. thanks the Science and Engineering Research Board
(SERB), New Delhi, India, for financial support and N.K.K.
thanks the CSIR, New Delhi, India, for a research fellowship.
Treanor, M.-J.; Schaub, R.; Bettinger, H. F. Angew. Chem., Int. Ed.
2015, 54, 8284−8286.
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